Admixture and method for improving hydraulic cement mixes

ABSTRACT

A hydraulic cement mix including hydraulic cement, aggregate, sufficient water to effect hydraulic setting of the cement, and an additive comprising a poly(hydroxyalkylated)polyethyleneamine or a poly(hydroxyethyl)polyethyleneimine or mixtures of each or both, the additive being present in an amount sufficient to increase the compressive strength of the hardened mix. Generally, the additive is present in a total amount of up to about 0.25% by weight based upon the weight of the cement, usually in an amount of between about 0.01% and about 0.25% by weight based upon the weight of the cement, preferably in an amount in the range of about 0.02% to about 0.07% by weight.

This application is a continuation-in-part of application of U.S. patent application Ser. No. 352,626 filed Feb. 26, 1982, now U.S. Pat. No. 4,401,472.

BACKGROUND OF THE INVENTION

This invention relates to additive compositions, otherwise known as admixtures, for incorporation in hydraulic cement mixes, for example, hydraulic cement concretes, mortars, and grouts, neat cement mixes, concrete block mixes, and dry mixes for making such concretes, mortars, and grouts, especially to increase the compressive strength of the hardened mix.

Admixtures are employed to achieve, among other things, water reduction, improved compressive strength, and retardation of the rate of hardening and setting of cement mixes. Frequently, greater compressive strengths are obtained when reduced quantities of water are utilized in hydraulic cement mixes, and so often water reduction and increased compressive strength are achieved together. Admixtures which increase compressive strength may also produce a retardation of the rate of set of the hydraulic cement mix. As retarders, such admixtures slow the chemical process of hydration so that the concrete remains plastic and workable for a longer time than concrete without such a retarder, which can result in increased hydration of the cement and ultimately increased compressive strengths. Although compressive strength improving admixtures can and usually do possess and produce additional features, they are valuable and desirable because of the increased compressive strength. Among the materials commonly used for improved compressive strength are the lignosulfonates, such as calcium lignosulfonate; salts of hydroxycarboxylic acids; sugars such as glucose (dextrose), maltose, sucrose, fructose, and the like; and highly polymerized polysaccharides, such as dextrins. These materials can produce additional results such as water reduction and/or retardation of the rate of set.

Other admixtures, known to increase the compressive strength of the hardened mix, also produce additional effects on the mix such as entraining air in the mix, or change the character of the mix, such as the stickiness or finishability of the mix. So, an admixture which could improve the compressive strength of the hardened mix without producing any other changes would be desirable.

Often, additives or admixtures are frequently used in combinations to achieve certain results or overcome inefficiencies or other features, such as where an admixture does produce a sufficient or significant improvement in the compressive strength, but also effects a significant degree of retardation. To overcome or compensate for these effects, whether desirable or not, such as for example, the excessive amount of retardation, well-known accelerators, such as calcium chloride and triethanolamine, that increase the rate of hydration for early strength development are frequently used. In addition, an admixture which increased compressive strength without affecting other features would be useful where the beneficial features of other admixtures could be combined to emphasize the additional other features. Thus, admixtures which can be used in combination with other admixtures are also desirable.

Further, the problem of unavailability would apply to any new and improved admixture. Increasing demands can make admixtures unavailable. Lignosulfonates, for example, are not as ubiquitously available as they once were due to the pressure of, among others, environmental restrictions which have forced suppliers to find means of consuming these materials through their own corporate channels. Also, sugars and dextrins are subject to the whims and fancies of speculative interests, and so have become quite costly, as well as occasionally being unavailable.

Thus a need exists for additive compositions, or admixtures, for incorporation in hydraulic cement mixes, which additives will provide improved compressive strength for the resulting cement products.

SUMMARY OF THE INVENTION

The present invention is an additive composition or admixture for incorporation in hydraulic cement mixes, such as concretes, mortars, and grouts, neat cement mixes, nonplastic cement mixes, and dry mixes for making concretes, mortars, and grouts and thus the improved cement mixes and process for incorporating the additive composition.

For the purposes of this invention, the term "hydraulic cement" is intended to mean and to include cementitious compositions capable of being set and hardened by the action of water, such as portland cements, sulphate-resisting cements, blast-furnace cements, pozzolanic cements, and high-alumina cements, since the additive composition or admixture of the present invention can be incorporated into all hydraulic cement mixes. But the preferred use of the present composition or admixture is in portland cement mixes. Also for the purposes of this invention, the term "portland cement" is intended to include all cementitious compositions which have a high content of tricalcium silicate and thus are portland cement or are chemically similar or analogous to and thus portland type cement, the specification for which is set forth in American Society for Testing and Materials specification (ASTM) C-150-80. This would include cements, in which fly ash, such as from steam or power generating stations, limestone, pozzolana slag, such as from blast furnaces, or mixtures of these, are incorporated and are considered portland cements, or portland blended cements such as those in ASTM C-595-79.

Broadly, the invention comprises a hydraulic cement mix including hydraulic cement, aggregate, sufficient water to effect hydraulic setting of the cement, and an additive comprising a poly(hydroxyalkylated)polyethyleneamine or mixtures thereof or a poly(hydroxyalkylated)polyethyleneimine or mixtures thereof or mixtures of both, said additive being present in an amount sufficient to increase the compressive strength of the hardened mix. The additive is preferably selected from N,N'-di-(hydroxyethyl)ethylenediamine, N,N,N'-tri-(hydroxyethyl)-ethylenediamine, N,N,N'-tri-(hydroxyethyl)diethylenetriamine, N,N,N',N'-tetra(hydroxyethyl)ethylenediamine, N,N,N',N',N'"-penta(hydroxyethyl)diethylenetriamine or poly(hydroxyethyl)polyethyleneimine. The additive is present in a total amount of up to about 1.0% by weight based upon the weight of the cement, generally in an amount of between about 0.005% and about 0.5% by weight based upon the weight of the cement, preferably in an amount in the range of about 0.01% to about 0.10% by weight, with the range 0.02% to about 0.07% also being a preferred range. Use of the additive is beneficial to the engineering properties of hydraulic cement mixes in that it generally results in products having an increased compressive strength over similar mixes prepared without the additive, generally without affecting the rate of hardening of the mix. Further, use of this additive in portland cements within the preferred ranges generally results in an increase in the compressive strength of the hardened hydraulic cement mixes.

It is therefore an object of the present invention to provide improved hydraulic cement mixes.

It is another object of this invention to provide improved hydraulic cement mixes, such as portland cement mixes, including concrete, mortar and grout mixes, neat cement mixes, nonplastic cement mixes, and dry mixes, which include an additive composition or admixture which will advantageously increase the compressive strength of the hardened cement mix.

These and other objects of the present invention will be readily apparent to those skilled in the art from the following detailed description and claims of the instant application.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the practice of the present invention, a poly(hydroxyalkylated)polyethyleneamine or a poly(hydroxyalkylated)polyethyleneimine or mixtures of each or both are incorporated in hydraulic cement mixes, such as portland cement concretes and mortars, high alumina cement concretes and mortars, and dry mixes for making such concretes and mortars in amounts sufficient to increase the compressive strength of the hardened hydraulic cement mix.

For the purpose of this application, the term poly(hydroxyalkylated)polyethyleneamine is defined as having the following general formula: ##STR1## wherein X is 1, 2 or 3; and R is selected from hydrogen, 2-hydroxyethyl, 2-hydroxypropyl, and each R can be the same or different, but at least 40% of the R groups must be hydroxyalkyl, with no more than 40% of the R groups being hydroxypropyl. An example of a poly(hydroxyalkylated)polyamine is tetra(hydroxyethyl)ethylenediamine (also known as N,N,N',N'-tetrakis-(2-hydroxyethyl)ethylenediamine or (HOCH₂ CH₂)₂ -NCH₂ CH₂ N-(CH₂ CH₂ OH)₂), which is a commercially available product and has known utility as an organic intermediate, in the crosslinking of rigid urethane foams, as a chelating agent, a humectant, a gas absorbent and in detergent processing. Other examples are N,N'-di(hydroxyethyl)-ethylenediamine; penta(hydroxyethyl)diethylenetriamine; and poly(hydroxyethyl)polyethyleneimine. An example of a poly(hydroxyalkyl)polyethyleneimine is poly(hydroxyethyl)polyethyleneimine, which is made by hydroxyalkylation of polyethyleneimine or by polymerization of N-hydroxyethylethyleneimine.

Broadly, the poly(hydroxyalkylated)polyethyleneamine or poly(hydroxyalkylated)polyethyleneimine will be incorporated in the cement mix in total amount of up to about 1.0% by weight based upon the weight of the cement, usually within the range of 0.01% to 0.1% by weight. A further preferred amount of the additive is 0.02% to 0.07% by weight, based upon the weight of the cement. The additive of the present invention is incorporated into hydraulic cement mixes preferably by adding it to a portion of the mix water used for mixing of the hydraulic cement and aggregate. But, the additive could be incorporated in any other convenient manner, including adding it to the dry mix before the water is incorporated therein.

The term aggregate is intended to include both fine aggregate, such as sand, and coarse aggregate, such as crushed stone or gravel, as is common in the art. In general for mortars, the aggregate may be sand or other fine aggregate meeting the requirements of ASTM standard C-33-80. The precise size, purity, quality, and quantity, or ranges thereof, of the fine and coarse aggregates will vary depending upon the desired use and properties of the mortar or concrete. For most common uses, although not limited thereto, the size of the fine aggregate will be within the broad range of about +4 mesh to -100 mesh U.S. Standard Sieve (ASTM C-11-70), while the size of the coarse aggregate will be within the broad range of 3 inches (7.6 cm) to 4 mesh. The coarse aggregate will usually be of mineral origin, such as gravel or crushed rock, but it may in some cases consist of at least partially of graded metallic material such as iron chips, or manufactured aggregate, such as slag.

Further in general for dry mortar mixes, the proportion of fine aggregate to cement will be in the range of about 25% to about 75% by weight based upon the weight of the cement mix, depending upon the nature of the aggregate and the desired properties and use of the mix.

For both the mortars and cements, the amount of water employed generally should be enough to effect hydraulic setting of the cement present in the mix and to provide suitable workability. This may broadly range from about 20% to 60% by weight of the cement in the mix for the mortars and about 25% to 70% by weight of the cement in the mix for the concretes. The precise amounts of water will depend upon the end use of the cement mix, as well as the aggregate and other admixtures present in the mix.

For purposes of illustrating the advantageous results obtainable by the practice of the present invention, plain cement mixes were prepared and compared with similar mixes in which various additives representative of the present invention were incorporated in varying dosages. The same type of cement was used in each mix, and the proportion and kind of aggregate employed were substantially the same. A sufficient amount of water was added to each mix to effect hydraulic setting of the cement mix and to produce cement mixes of essentially the same consistency. The tests from which the results were derived were those commonly employed and standardized in the ASTM standards for testing cement and/or concrete mixes, including ASTM standards C-39-72 (1979), C-143-78, C-231-78, C-403-77, all of which are incorporated herein by reference. In addition and for the purpose of further illustrating the invention, comparisons were made with diethanolamine and triethanolamine which are known and commercially available as additives or admixtures and which are known to increase the strength of a hardened concrete mix.

                                      TABLE I                                      __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     SERIES A                                                                       Cement No. 1                                                                    1   NONE  0        324    1.8   0 (63/8)                                                                             0 (83/4)                                                                            619 2288                                                                               3619                                           (192)                   (4.3)                                                                              (15.8)                                                                             (24.9)                      2   A     .01      315    1.9   -1/4  -1/2 651 2335                                                                               4005                                           (187)                   (4.5)                                                                              (16.1)                                                                             (27.6)                      3   A     .025     311    2.0   -1/8  -3/8 638 2394                                                                               4325                                           (184)                   (4.4)                                                                              (16.5)                                                                             (29.8)                      4   A     .05      311    2.2   0     -3/8 632 2416                                                                               4385                                           (184)                   (4.3)                                                                              (16.6)                                                                             (30.2)                      5   A     .1       311    2.5   +1/8  -1/4 625 2460                                                                               3972                                           (184)                   (4.3)                                                                              (16.9)                                                                             (27.4)                      6   DEA   .1       313    1.9   -1/2  -3/4 666 2638                                                                               4405                                           (186)                   (4.6)                                                                              (18.2)                                                                             (30.4)                      7   TEA   .025     315    1.9   -5/8  -3/4 742 2744                                                                               4470                                           (187)                   (5.1)                                                                              (18.9)                                                                             (30.8)                     SERIES A                                                                       Cement No. 2                                                                    8   NONE  0        327    1.7   0 (63/4)                                                                             0 (91/8)                                                                            600 2184                                                                               3607                                           (194)                   (4.1)                                                                              (15.0)                                                                             (24.9)                      9   A     .01      318    1.8   0     +1/8 619 2235                                                                               3821                                           (189)                   (4.3)                                                                              (15.4)                                                                             (26.3)                     10   A     .025     316    1.8   +1/4  +1/8 625 2281                                                                               4246                                           (187)                   (4.3)                                                                              (15.7)                                                                             (29.3)                     11   A     .05      315    2.0   0     +3/8 623 2363                                                                               4435                                           (187)                   (4.3)                                                                              (16.3)                                                                             (30.6)                     12   A     .1       310    2.9   0     +1/4 614 2488                                                                               4321                                           (184)                   (4.2)                                                                              (17.1)                                                                             (29.8)                     13   DEA   .1       312    2.2   -3/8  -3/4 672 2475                                                                               4435                                           (185)                   (4.6)                                                                              (17.0)                                                                             (30.6)                     14   TEA   .025     320    1.9   -5/8  -3/4 716 2538                                                                               3949                                           (190)                   (4.9)                                                                              (17.5)                                                                             (27.2)                     SERIES B                                                                       Cement No. 1                                                                   15   NONE  0        317    2.0   0 (57/8)                                                                             0 (83/8)                                                                            617 2399                                                                               3555                                           (188)                   (4.2)                                                                              (16.5)                                                                             (24.5)                     16   A     .025     310    2.5   -1/4  -3/8 673 2687                                                                               4371                                           (184)                   (4.6)                                                                              (18.5)                                                                             (30.1)                     17   A + TEA                                                                              .025 + .015                                                                             311    2.8   -5/8  -7/8 704 2668                                                                               4258                                           (184)                   (4.8)                                                                              (18.4)                                                                             (29.5)                     SERIES B                                                                       Cement No. 2                                                                   18   NONE  0        325    1.7   0 (61/8)                                                                             0 (85/8)                                                                            573 2026                                                                               3494                                           (193)                   (3.9)                                                                              (14.0)                                                                             (24.1)                     19   A     .025     321    2.0   -1/8  -3/8 632 2394                                                                               4126                                           (190)                   (4.3)                                                                              (16.5)                                                                             (28.4)                     20   A + TEA                                                                              .025 + .015                                                                             318    2.2   -1/2  -1   657 2405                                                                               4118                                           (189)                   (4.5)                                                                              (16.6)                                                                             (28.4)                     SERIES C                                                                       Cement No. 1                                                                   21   NONE  0        318    1.9   0 (63/8)                                                                             0 (8 7/8)                                                                           616 2255                                                                               3905                                           (189)                   (4.2)                                                                              (15.5)                                                                             (26.9)                     22   A     .025     308    2.4   -1/8  -3/8 636 2320                                                                               4357                                           (183)                   (4.4)                                                                              (16.0)                                                                             (30.0)                     23   A     .05      307    2.7   -1/8  -3/8 648 2492                                                                               4561                                           (182)                   (4.5)                                                                              (17.2)                                                                             (31.4)                     24   A     .075     305    2.7   -1/8  -3/8 662 2413                                                                               4442                                           (181)                   (4.6)                                                                              (16.6)                                                                             (30.6)                     25   B     .025     304    2.7     -1/16                                                                              -3/8 636 2362                                                                               4451                                           (180)                   (4.4)                                                                              (16.2)                                                                             (30.7)                     26   B     .05      303    3.0   -1/8  -1/2 648 2451                                                                               4602                                           (180)                   (4.4)                                                                              (16.9)                                                                             (31.7)                     27   B     .075     303    3.0   0     -1/2 640 2376                                                                               4549                                           (180)                   (4.4)                                                                              (16.4)                                                                             (31.4)                     SERIES C                                                                       Cement No. 2                                                                   28   NONE  0        313    2.0   0 (61/4)                                                                             0 (85/8)                                                                            573 2317                                                                               3637                                           (186)                   (3.9)                                                                              (16.0)                                                                             (25.1)                     29   A     .025     297    2.9   -1/4  -1/4 607 2501                                                                               4219                                           (176)                   (4.2)                                                                              (17.2)                                                                             (29.1)                     30   A     .05      297    3.1   0     -1/4 600 2553                                                                               4335                                           (176)                   (4.1)                                                                              (17.6)                                                                             (29.9)                     31   A     .075     295    3.4     -1/16                                                                              -3/8 619 2570                                                                               4374                                           (175)                   (4.3)                                                                              (17.7)                                                                             (30.1)                     32   B     .025     301    2.9   -1/8  -1/4 592 2509                                                                               4348                                           (179)                   (4.1)                                                                              (17.3)                                                                             (30.0)                     33   B     .05      296    3.2   -1/8  -1/4 601 2519                                                                               4377                                           (176)                   (4.1)                                                                              (17.4)                                                                             (30.2)                     34   B     .075     298    3.4     +1/16                                                                              -1/2 626 2540                                                                               4375                                           (177)                   (4.4)                                                                              (17.5)                                                                             (30.2)                     SERIES D                                                                       Cement No. 1                                                                   35   NONE  0        324    1.6   0 (63/8)                                                                             0 (87/8)                                                                            663 2254                                                                               3660                                           (192)                   (4.6)                                                                              (15.5)                                                                             (25.2)                     36   B     .005     317    2.0   -1/4  -1/2 686 2341                                                                               3921                                           (188)                   (4.7)                                                                              (16.1)                                                                             (27.0)                     37   B     .01      311    2.0   -1/4  -1/2 713 2444                                                                               4128                                           (184)                   (4.9)                                                                              (16.8)                                                                             (28.4)                     38   B     .025     313    2.1   -1/4  -3/8 694 2365                                                                               4169                                           (186)                   (4.8)                                                                              (16.3)                                                                             (28.7)                     39   B     .05      308    2.6   -1/4  -1/2 686 2443                                                                               4444                                           (183)                   (4.7)                                                                              (16.8)                                                                             (30.6)                     40   B     .1       307    2.9   -3/8  -3/4 676 2522                                                                               4310                                           (182)                   (4.7)                                                                              (17.4)                                                                             (29.7)                     41   B     .25      301    4.0   -1/4  -3/8 610 2701                                                                               4443                                           (179)                   (4.2)                                                                              (18.6)                                                                             (30.6)                     42   DEA   .025     316    1.9   -1/4  -3/8 635 2328                                                                               3823                                           (187)                   (4.4)                                                                              (16.0)                                                                             (26.3)                     43   DEA   .05      314    2.1   -3/8  --5/8                                                                               624 2413                                                                               4048                                           (186)                   (4.3)                                                                              (16.6)                                                                             (27.9)                     44   DEA   .1       313    2.3   -1/2  -5/8 604 2576                                                                               4287                                           (186)                   (4.2)                                                                              (17.7)                                                                             (29.5)                     SERIES D                                                                       Cement No. 2                                                                   45   NONE  0        323    1.6   0 (67/8)                                                                             0 (91/2)                                                                            558 2202                                                                               3679                                           (192)                   (3.8)                                                                              (15.2)                                                                             (25.4)                     46   B     .005     312    1.9   -1/8  -1/8 602 2301                                                                               3797                                           (185)                   (4.1)                                                                              (15.9)                                                                             (26.2)                     47   B     .01      312    1.9   -1/4  -1/8 581 2323                                                                               3801                                           (185)                   (4.0)                                                                              (16.0)                                                                             (26.2)                     48   B     .025     308    2.1   0     -1/8 633 2360                                                                               4052                                           (183)                   (4.4)                                                                              (16.3)                                                                             (27.9)                     49   B     .05      311    2.2   -1/8  -1/8 657 2405                                                                               4099                                           (184)                   (4.5)                                                                              (16.6)                                                                             (28.2)                     50   B     .1       303    2.7   -1/4  -5/8 716 2635                                                                               4361                                           (180)                   (4.9)                                                                              (18.2)                                                                             (30.1)                     51   B     .25      302    3.4   -1/8  -1/8 685 2639                                                                               4091                                           (179)                   (4.7)                                                                              (18.2)                                                                             (28.2)                     52   DEA   .025     312    1.9   -1/4  -1/4 594 2360                                                                               3910                                           (185)                   (4.1)                                                                              (16.3)                                                                             (26.9)                     53   DEA   .05      312    1.8   -1/4  -3/4 638 2457                                                                               3846                                           (185)                   (4.4)                                                                              (16.9)                                                                             (26.5)                     54   DEA   .1       312    1.8   0     -1/8 604 2439                                                                               3893                                           (185)                   (4.2)                                                                              (16.8)                                                                             (26.8)                     __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE II                                     __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     Cement No. 1                                                                   55   NONE  0        315    1.5   0 (53/4)                                                                             0 (83/8)                                                                            628 2188                                                                               3688                                           (187)                   (4.3)                                                                              (15.1)                                                                             (25.4)                     56   C     .025     316    1.8   +1/4  +1/4 664 2269                                                                               4063                                           (187)                   (4.6)                                                                              (15.6)                                                                             (28.0)                     57   C     .05      315    2.1   +1/4  +5/8 644 2250                                                                               4369                                           (187)                   (4.4)                                                                              (15.5)                                                                             (30.1)                     58   B     .025     313    2.0   +1/2  +1   663 2250                                                                               4088                                           (186)                   (4.6)                                                                              (15.5)                                                                             (28.2)                     59   B     .05      310    2.4   +3/8  +1/2 638 2285                                                                               4357                                           (184)                   (4.4)                                                                              (15.7)                                                                             (30.0)                     Cement No. 2                                                                   60   None  0        325    1.2   0 (63/8)                                                                             0 (9)                                                                               557 2287                                                                               3363                                           (193)                   (3.8)                                                                              (15.8)                                                                             (23.2)                     61   C     .025     323    1.4   +1/8  +1/2 599 2394                                                                               3801                                           (192)                   (4.1)                                                                              (16.5)                                                                             (26.2)                     62   C     .05      320    1.6   0     +1/4 602 2368                                                                               3898                                           (190)                   (4.1)                                                                              (16.3)                                                                             (26.9)                     63   B     .025     321    1.4   +1/4  +3/8 594 2469                                                                               3644                                           (190)                   (4.1)                                                                              (17.0)                                                                             (25.1)                     64   B     .05      313    1.8   +3/8  +1/8 593 2510                                                                               3735                                           (186)                   (4.1)                                                                              (17.3)                                                                             (25.7)                     __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE III                                    __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     SERIES A                                                                       Cement No. 1                                                                   65   NONE  0        322    1.8   0 (63/8)                                                                             0 (87/8)                                                                            618 2257                                                                               3538                                           (191)                   (4.3)                                                                              (15.5)                                                                             (24.4)                     66   D     .01      314    2.3   -1/4  -1/4 691 2399                                                                               4135                                           (186)                   (4.8)                                                                              (16.5)                                                                             (28.5)                     67   D     .025     316    2.5   +1/4  -1/8 643 2350                                                                               4243                                           (187)                   (4.4)                                                                              (16.2)                                                                             (29.2)                     68   D     .05      309    3.1   0     -1/8 656 2461                                                                               4543                                           (183)                   (4.5)                                                                              (17.0)                                                                             (31.3)                     69   D     .075     313    2.8   0     0    665 2507                                                                               4554                                           (186)                   (4.6)                                                                              (17.3)                                                                             (31.4)                     70   A     .025     311    2.9   -1/8  -1/4 688 2432                                                                               4540                                           (184)                   (4.7)                                                                              (16.8)                                                                             (31.3)                     71   A     .05      311    2.9   0     -1/4 669 2407                                                                               4463                                           (184)                   (4.6)                                                                              (16.6)                                                                             (30.8)                     72   TEA   .025     315    2.6   -1    - 11/8                                                                              785 2623                                                                               4307                                           (187)                   (5.4)                                                                              (18.1)                                                                             (29.7)                     SERIES A                                                                       Cement No. 2                                                                   73   NONE  0        317    2.1   0 (6) 0 (81/2)                                                                            508 2238                                                                               3425                                           (188)                   (3.5)                                                                              (15.4)                                                                             (23.6)                     74   D     .01      312    2.8   0     0    583 2294                                                                               3569                                           (185)                   (4.0)                                                                              (15.8)                                                                             (24.6)                     75   D     .025     310    3.2   0     +1/8 585 2362                                                                               3869                                           (184)                   (4.0)                                                                              (16.3)                                                                             (26.7)                     76   D     .05      306    3.4   0     +1/4 576 2565                                                                               4038                                           (182)                   (4.0)                                                                              (17.7)                                                                             (27.8)                     77   D     .075     303    3.6   0     0    628 2655                                                                               4120                                           (180)                   (4.3)                                                                              (18.3)                                                                             (28.4)                     78   A     .025     306    3.1   +1/8  0    616 2411                                                                               3961                                           (182)                   (4.2)                                                                              (16.6)                                                                             (27.3)                     79   A     .05      303    3.6   0     +3/8 644 2515                                                                               4068                                           (180)                   (4.4)                                                                              (17.3)                                                                             (28.0)                     80   TEA   .025     304    3.3   -3/4  -7/8 656 2435                                                                               3768                                           (180)                   (4.5)                                                                              (16.8)                                                                             (26.0)                     SERIES B                                                                       Cement No. 1                                                                   81   NONE  0        319    1.7   0 (6) 0 (81/2)                                                                            629 2200                                                                               3598                                           (189)                   (4.3)                                                                              (15.2)                                                                             (24.8)                     82   E     .01      319    1.5   0     +1/4 665 2394                                                                               3840                                           (189)                   (4.6)                                                                              (16.5)                                                                             (26.5)                     83   E     .025     312    1.9   0     0    678 2344                                                                               4160                                           (185)                   (4.7)                                                                              (16.1)                                                                             (28.7)                     84   E     .05      316    1.9   +1/8  +1/4 668 2313                                                                               4144                                           (187)                   (4.6)                                                                              (15.9)                                                                             (28.6)                     85   F     .01      312    1.8   +1/8  0    706 2446                                                                               4090                                           (185)                   (4.9)                                                                              (16.9)                                                                             (28.2)                     86   F     .025     308    2.0   +1/8  -1/8 690 2471                                                                               4365                                           (183)                   (4.7)                                                                              (17.0)                                                                             (30.1)                     87   F     .05      314    2.0   0     +1/8 669 2397                                                                               4093                                           (186)                   (4.6)                                                                              (16.5)                                                                             (28.2)                     88   A     .025     317    1.9   +1/8  +1/8 676 2375                                                                               4223                                           (188)                   (4.7)                                                                              (16.4)                                                                             (29.1)                     89   A     .05      318    2.0   +1/8  0    669 2416                                                                               4294                                           (189)                   (4.6)                                                                              (16.6)                                                                             (29.6)                     90   B     .025     314    1.8   +3/8  +1/8 663 2238                                                                               4244                                           (186)                   (4.6)                                                                              (15.4)                                                                             (29.2)                     91   B     .05      316    1.9   0     -1/8 638 2280                                                                               4175                                           (187)                   (4.4)                                                                              (15.7)                                                                             (28.8)                     SERIES B                                                                       Cement No. 2                                                                   92   NONE  0        320    1.6   0 (61/4)                                                                             0 (83/4)                                                                            568 2332                                                                               3516                                           (190)                   (3.9)                                                                              (16.1)                                                                             (24.2)                     93   E     .01      318    1.5   -1/4  -5/8 587 2379                                                                               3628                                           (189)                   (4.0)                                                                              (16.4)                                                                             (25.0)                     94   E     .025     314    1.7   -1/4  -3/4 648 2566                                                                               4112                                           (186)                   (4.5)                                                                              (17.7)                                                                             (28.3)                     95   E     .05      315    1.7   -1/8  -1/2 637 2550                                                                               4133                                           (187)                   (4.4)                                                                              (17.6)                                                                             (28.5)                     96   F     .01      311    1.4   -1/4  -1/2 623 2544                                                                               3941                                           (184)                   (4.3)                                                                              (17.5)                                                                             (27.2)                     97   F     .025     314    1.6   -1/8  -1/2 622 2616                                                                               4105                                           (186)                   (4.3)                                                                              (18.0)                                                                             (28.3)                     98   F     .05      310    2.0   +1/4  -3/4 646 2585                                                                               4160                                           (184)                   (4.4)                                                                              (17.8)                                                                             (28.7)                     99   A     .025     312    1.8   -1/4  -7/8 669 2613                                                                               4167                                           (185)                   (4.6)                                                                              (18.0)                                                                             (28.7)                     100  A     .05      312    1.8   -1/4  -3/4 688 2616                                                                               4243                                           (185)                   (4.7)                                                                              (18.0)                                                                             (29.2)                     101  B     .025     313    1.6   0     -1/2 643 2507                                                                               4194                                           (186)                   (4.4)                                                                              (17.3)                                                                             (28.9)                     102  B     .05      312    1.9   -1/4  -1/2 667 2652                                                                               4155                                           (185)                   (4.6)                                                                              (18.3)                                                                             (28.6)                     SERIES C                                                                       Cement No. 1                                                                   103  NONE  0        318    1.6   0 (61/8)                                                                             0 (81/2)                                                                            666 2275                                                                               3804                                           (189)                   (4.6)                                                                              (15.7)                                                                             (26.2)                     104  G     .01      317    2.1   0     0    643 2257                                                                               4040                                           (188)                   (4.4)                                                                              (15.5)                                                                             (27.8)                     105  G     .025     311    2.5   -1/4  -3/8 696 2435                                                                               4451                                           (184)                   (4.8)                                                                              (16.8)                                                                             (30.7)                     106  G     .05      308    2.7   -1/4  -1/4 664 2493                                                                               4430                                           (183)                   (4.6)                                                                              (17.2)                                                                             (30.5)                     107  G     .10      312    2.5   -3/8  -3/8 638 2510                                                                               4435                                           (185)                   (4.4)                                                                              (17.3)                                                                             (30.6)                     108  B     .05      312    2.6   +1/8  0    629 2262                                                                               4179                                           (185)                   (4.3)                                                                              (15.6)                                                                             (28.8)                     109  C     .05      317    2.2   -1/4  -1/2 685 2327                                                                               4050                                           (188)                   (4.7)                                                                              (16.0)                                                                             (27.9)                     SERIES C                                                                       Cement No. 2                                                                   110  NONE  0        322    1.6   0 (61/4)                                                                             0 (83/4)                                                                            575 2374                                                                               3603                                           (191)                   (4.0)                                                                              (16.4)                                                                             (24.8)                     111  G     .01      319    1.7   -1/8  -1/8 524 2345                                                                               3711                                           (189)                   (3.6)                                                                              (16.2)                                                                             (25.6)                     112  G     .025     312    2.0   -1/4  -1/2 580 2530                                                                               4269                                           (185)                   (4.0)                                                                              (17.4)                                                                             (29.4)                     113  G     .05      311    2.1   -1/4  -1/2 627 2562                                                                               4365                                           (184)                   (4.3)                                                                              (17.7)                                                                             (30.1)                     114  G     .10      307    2.3   -3/8  -7/8 650 2780                                                                               4496                                           (182)                   (4.5)                                                                              (19.2)                                                                             (31.0)                     115  B     .05      303    2.1   -3/8  -5/8 585 2711                                                                               4402                                           (180)                   (4.0)                                                                              (18.7)                                                                             (30.3)                     116  C     .05      307    2.1   -1/2  -3/4 577 2744                                                                               4480                                           (182)                   (4.0)                                                                              (18.9)                                                                             (30.9)                     SERIES D                                                                       Cement No. 1                                                                   117  NONE  0        325    1.9   0 (6) 0 (81/2)                                                                            636 2144                                                                               3690                                           (193)                   (4.4)                                                                              (14.8)                                                                             (25.4)                     118  H     .01      317    3.5   +1/4  -1/8 625 2057                                                                               3768                                           (188)                   (4.3)                                                                              (14.2)                                                                             (26.0)                     119  H     .025     309    4.2   -1/8  -1/4 631 2137                                                                               3898                                           (183)                   (4.3)                                                                              (14.7)                                                                             (26.9)                     120  H     .05      305    4.8   0     0    636 2132                                                                               3869                                           (181)                   (4.4)                                                                              (14.7)                                                                             (26.7)                     121  H     .10      303    4.8   +1/4  -1/4 642 2132                                                                               4146                                           (180)                   (4.4)                                                                              (14.7)                                                                             (28.6)                     122  I     .01      317    3.5   +1/8  -1/8 584 1994                                                                               3764                                           (188)                   (4.0)                                                                              (13.7)                                                                             (25.9)                     123  I     .025     306    4.7   +1/8  0    659 2009                                                                               3795                                           (182)                   (4.5)                                                                              (13.8)                                                                             (26.2)                     124  I     .05      303    5.0   +1/8  -1/8 660 2094                                                                               4043                                           (180)                   (4.5)                                                                              (14.4)                                                                             (27.9)                     125  I     .10      303    4.9   0     0    662 2056                                                                               4183                                           (180)                   (4.6)                                                                              (14.2)                                                                             (28.8)                     126  B     .05      317    2.9   +1/4  +1/8 593 2169                                                                               4040                                           (188)                   (4.1)                                                                              (14.9)                                                                             (27.8)                     SERIES D                                                                       Cement No. 2                                                                   127  NONE  0        328    1.8   0 (71/8)                                                                             0 (97/8)                                                                            388 2065                                                                               3198                                           (195)                   (2.7)                                                                              (14.2)                                                                             (22.0)                     128  H     .01      314    3.2   -1/8  0    394 2144                                                                               3226                                           (186)                   (2.7)                                                                              (14.8)                                                                             (22.2)                     129  H     .025     307    3.9   0     -1/8 413 2174                                                                               3494                                           (182)                   (2.8)                                                                              (15.0)                                                                             (24.1)                     130  H     .05      308    4.2   0     -1/8 406 2260                                                                               3410                                           (183)                   (2.8)                                                                              (15.6)                                                                             (23.5)                     131  H     .10      307    4.3   0     0    419 2268                                                                               3649                                           (182)                   (2.9)                                                                              (15.6)                                                                             (25.1)                     132  I     .01      314    3.3   -1/2  -3/8 403 2191                                                                               3338                                           (186)                   (2.8)                                                                              (15.1)                                                                             (23.0)                     133  I     .025     310    4.2   -1/8  -1/4 419 2168                                                                               3463                                           (184)                   (2.9)                                                                              (14.9)                                                                             (23.9)                     134  I     .05      304    4.3   - 1/4 -1/8 406 2207                                                                               3835                                           (180)                   (2.8)                                                                              (15.2)                                                                             (26.4)                     135  I     .10      305    4.6   -1/8  -1/4 419 2220                                                                               3883                                           (181)                   (2.9)                                                                              (15.3)                                                                             (26.8)                     136  B     .05      321    2.3   +1/8  -1/4 407 2143                                                                               3790                                           (190)                   (2.8)                                                                              (14.8)                                                                             (26.1)                     __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE IV                                     __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     Cement No. 1                                                                   137  NONE  0        319    2.1   0 (61/8)                                                                             0 (81/4)                                                                            616 2175                                                                               3619                                           (189)                   (4.2)                                                                              (15.0)                                                                             (24.9)                     138  J     .01      313    2.5   +1/8  +1/4 631 2219                                                                               3769                                           (186)                   (4.3)                                                                              (15.3)                                                                             (26.0)                     139  J     .025     310    2.5   -1/8  +1/4 646 2318                                                                               4113                                           (184)                   (4.4)                                                                              (16.0)                                                                             (28.3)                     140  J     .05      300    3.2   0     -1/4 669 2552                                                                               4316                                           (178)                   (4.6)                                                                              (17.6)                                                                             (29.7)                     141  J     .10      294    5.2   0     +1/4 672 2387                                                                               4066                                           (174)                   (4.6)                                                                              (16.4)                                                                             (28.0)                     Cement No. 2                                                                   142  NONE  0        327    1.4   0 (61/4)                                                                             0 (83/4)                                                                            419 1926                                                                               3210                                           (194)                   (2.9)                                                                              (13.3)                                                                             (22.1)                     143  J     .01      321    1.5   -1/8  +1/8 422 1974                                                                               3302                                           (190)                   (2.9)                                                                              (13.6)                                                                             (22.8)                     144  J     .025     318    2.0   +1/8  +1/8 444 1962                                                                               3382                                           (189)                   (3.1)                                                                              (13.5)                                                                             (23.3)                     145  J     .05      306    3.1   +1/8  0    454 2137                                                                               3670                                           (182)                   (3.1)                                                                              (14.7)                                                                             (25.3)                     146  J     .10      301    4.2   -1/8  0    463 2243                                                                               3739                                           (179)                   (3.2)                                                                              (15.5)                                                                             (25.8)                     __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

The results shown in Tables I, II, III and IV illustrate generally the use of the admixture in accordance with the present invention in two Type I portland cement mixes (where the cements were from two different manufacturers) to form concretes. For convenience, the tests were run as a series of tests wherein the dosages were varied, and comparisons were made with a plain (no admixture) concrete mix. The fine aggregate to coarse aggregate ratio was between 0.46 and 0.47, the amount of cement was 420 lbs. per cubic yard (249 kg. per cubic meter) of concrete, and the consistencies of the concretes (measured as "slump" in accordance with ASTM C 143-78) were such that the mixes had slumps of 5 inches ±1/2 inch (12.7 cm. ±1.3 cm.). In each case the mix is a single mix, except in Table I, Series C, where the tests were duplicated for verification and so, for convenience, the results reported are the average of the two mixes. In each series the rate of set is shown relative to the plain mix in that series. The actual rate of set of the plain mix is shown parenthetically.

In the Tables, DEA and TEA are commercially available alkanolamines, namely diethanolamine and triethanolamine, respectively, whereas additives A through J are identified as follows:

A--Tetra(hydroxyethyl)ethylenediamine

B--Tetra(hydroxyethyl)ethylenediamine

C--Tetra(hydroxyethyl)ethylenediamine

D--N,N,N'-tri-(hydroxyethyl)ethylenediamine

E--N,N,N'-tri-(hydroxyethyl)diethylenetriamine

F--Penta-(hydroxyethyl)diethylenetriamine

G--N,N'-di-(hydroxyethyl)ethylenediamine

H--N,N'-bis(2-hydroxypropyl)-diethylenetriamine

I--Bis-(2-hydroxypropyl)-tri-(hydroxyethyl)diethylenetriamine

J--Poly(hydroxyethyl)polyethyleneimine

Additives A, B and C are the same, except that A and B are from different commercial sources, while C was produced in the laboratory, as will be described hereinafter. All the other poly(hydroxyalkylated)polyethyleneamines were purchased, except for additive H, which also was manufactured, as will be described hereinafter. While most of the additives were purchased, all of the poly(hydroxyalkylated)polyethyleneamines contemplated by this invention could be manufactured in the manner described herein. The poly(hydroxyalkylated)polyethyleneimine also was manufactured in the laboratory, as will be described hereinafter.

Tetra(hydroxyethyl)ethylenediamine was manufactured as follows:

A multi-necked 1-liter round bottom flask, was charged with 203.7 gm (3.39 moles) ethylene diamine and 160 gm water. The flask was fitted with a thermometer, overhead stirrer, dry ice condenser and a gas dispersing tube below the liquid surface. Ethylene oxide was introduced through the dispersing tube until 600 gm (13.6 moles) was added to the mixture and reacted with the ethylenediamine. The mixture was continuously stirred throughout the ethoxylation step. The temperature throughout this period was maintained at 20° C.-40° C. The resulting product was a water solution comprising 83% by weight tetra(hydroxyethyl)ethylenediamine with the appearance of a clear homogeneous syrup. An aliquot of the product solution was high vacuum dried and characterized by infra-red and Nuclear Magnetic Resonance Spectra. Both the infra-red spectra and the Nuclear Magnetic Resonance Spectra indicated that the manufactured material was essentially identical to the commercial material. The N,N'-[bis(2-hydroxypropyl)]-N,N',N"-[tri(hydroxyethyl)]diethylenetriamine was manufactured using the same equipment mentioned above, with the addition of a 125 ml dropping funnel. The following was the precedent: The flask was charged with 352.8 gm (3.42 moles) of diethylenetriamine. Next, 417 gm (7.18 moles) of propylene oxide was added gradually through the dropping funnel while maintaining the reaction temperature at between about 30° C. and 45° C. This produces N,N'-bis(2-hydroxypropyl)diethylenetriamine, which itself is usable as an additive in accordance with the present invention and which was then subjected to the same ethoxylation step described above by introducing 75 gm of water and then 180 gm (4.09 moles) of ethylene oxide. The resulting product is the mixed poly(hydroxyalkylated)polyethyleneamine.

Poly(hydroxyalkylated)polyethyleneimines, such as poly(hydroxyethyl)polyethyleneimine, can be manufactured in the same equipment and ethoxylation method mentioned above. In that process, polyethyleneimine, which is commercially available in a variety of molecular weights, is subjected to ethoxylation. The precise molecular weight of the polyethyleneamine is not critical. In manufactured material used herein, the polyethyleneimine had a molecular weight of 600. Another source had a molecular weight of 1200.

As can be seen from Table I, the use of tetra(hydroxyethyl)ethylenediamine in accordance with the present invention produces an increased strength gain, especially at the later ages, e.g., 28 days. In mixes 5 and 12, a substantial amount of air was observed coming from the surface of the concrete mix--this could also be called unstable air--but as seen from the data in Table I, the mixes did not result in excessive entrained air and did result in beneficial 28-day strength gains. Further, as seen from the data in Table I, Series D, later tests at the same and higher doses did not produce excessive or unstable air. So although it was not explained, it was not felt to be a problem. Still further, the combination of tetra(hydroxyethyl)ethylenediamine with TEA can produce both an acceleration of the rate of setting and hardening and an improved early (one day) compressive strength. Thus, tetra(hydroxyethyl)ethylenediamine would be useful in combination with other admixtures. The results in Table II demonstrate that the laboratory synthesized or manufactured tetra(hydroxylethyl)ethylenediamine performs equivalently to the purchased product. The tests in Table III illustrate that other poly(hydroxyalkylated)polyamines are useful in increasing the compressive strength of hardened concrete mixes. The results in Table IV demonstrate that poly(hydroxyalkylated)polyethyleneimines are also useful in improving compressive strength in hardened concrete.

Additionally, it has been discovered that additional poly(hydroxyalkylated)polyamines can act as compressive strength enhancers which do not meet the general formula set forth hereinabove. These structures differ generally in the separation of the amine sites and the extended alkoxylation of hydroxyl sites. Such materials could be defined by the general formula:

    (R').sub.2 NCH.sub.2 CH.sub.2 N(R').sub.2

wherein R' is (CH₂ CH₂ O)_(y) H, wherein y is selected from 0, 1 or 2, wherein no more than one-half (1/2) of the y's are equal to 0. Additionally, the R' on one end of the structure need not be identical to the R' on the other end of the structure.

Examples of such materials include: the condensate of an 8 to 1 mole ratio of propylene oxide to diethylenetriamine; the condensate of a 5 to 1 mole ratio of ethylene oxide to ethylenediamine; the condensate of a 6 to 1 mole ratio of ethylene oxide to ethylenediamine; the condensate of an 8 to 1 mole ratio of ethylene oxide to ethylenediamine; and the condensate of an 8 to 1 mole ratio of ethylene oxide to ethylenetriamine.

Additionally it has been discovered that derivatives of hydrazine, 1,2-diaminopropane and polyglycoldiamine can act as compressive strength enhancers which do not meet either of the general formulae set forth hereinabove. These materials can be defined by the general formula: ##STR2## wherein R" is selected from the group of (CH₂ CH₂ O)_(y) H and ##STR3## wherein X is a covalent bond or a divalent organic radical selected from the group of CH₂, CH₂ CH₂, ##STR4## and CH₂ CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ CH₂ ;

wherein y and v are selected from the group of 0, 1 and 2;

wherein w is selected from the group of 0 and 1;

wherein v and w cannot both be 0; and

wherein no more than one-half (1/2) of the R" groups are hydrogen.

Examples of such materials include: di(hydroxyethyl)1,2-diaminopropane; tetra(hydroxyethyl)1,2-diaminopropane; di(hydroxyethyl)hydrazine; tetra(hydroxyethyl)hydrazine; ethoxylated polyglycoldiamine; and the condensate of 2 to 1 mole ratio of diethanolamine to formaldehyde.

The Tables V through XVII below illustrate the use of these materials in accordance with the concepts of the present invention to obtain the benefits thereof. In the tables below, the additives identified below are in addition to those materials already identified above and used in Tables I through IV. These materials are identifed as follows:

K--8:1 mole ratio of propyleneoxide to diethylenetriamine commercially available from Dow Chemical under the trademark Voranol 202

L--di(hydroxyethyl) 1,2-diaminopropane

M--tetra(hydroxyethyl)1,2-diaminopropane

N--di(hydroxyethyl)hydrazine

O--tetra(hydroxyethyl)hydrazine

P--5:1 mole ratio of ethylene oxide to ethylenediamine

Q--6:1 mole ratio of ethylene oxide to ethylenediamine

R--8:1 mole ratio of ethylene oxide to ethylenediamine

S--ethoxylated polyglycoldiamine

T--an ethoxylated amine commercially available from Union Carbide Corporation under the trademark Ethoxylated Amine HH which when ethoxylated yields a typical analysis of: ##STR5## U--2:1 mole ratio of diethanolamine to formaldehyde All of these materials were purchased as commercially available materials.

                                      TABLE V                                      __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     147  NONE  0        324    1.5   0 (6) 0 (81/4)                                                                            644 2321                                                                               3510                       148  K     .01      295    3.8   -1/8  +1/8 757 2677                                                                               3979                       149  K     .02      294    4.2   0     +1/4 743 2570                                                                               3910                       150  K     .03      296    4.1   0     +1/4 733 2499                                                                               3846                       151  K + TEA                                                                              .02 + .015                                                                              300    4.0   +5/8  -7/8 828 2521                                                                               3985                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE VI                                     __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     152  NONE  0        321    1.8   0 (6) 0 (8)                                                                               668 2399                                                                               3819                       153  K     .01      297    3.0   -5/8  -1/2 859 2827                                                                               3988                       154  K     .025     295    3.2   -1/2  -1/2 905 2916                                                                               4044                       155  K     .05      293    3.8   -5/8  -1/2 880 2862                                                                               4043                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE VII                                    __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     156  NONE  0        324    1.9   0 (6) 0 (8)                                                                               649 2235                                                                               3613                       157  L     .015     319    2.3   0     +1/4 682 2327                                                                               3913                       158  L     .025     317    2.4   0     -1/4 758 2426                                                                               4044                       159  L + TEA                                                                              .025 + .01                                                                              319    2.6   -1/2  -3/8 765 2438                                                                               4252                       160  O     .025     319    2.3   0     -1/4 704 2363                                                                               3868                       161  O + TEA                                                                              .025 + .01                                                                              321    2.4   -1/2  -3/8 782 2371                                                                               3929                       162  O     .05      316    2.4   -1/4  -1/8 719 2464                                                                               4028                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (- )          sign, while retardation is indicated by a plus (+) sign.                 

                                      TABLE VIII                                   __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     163  NONE  0        310    2.0   0 (61/4)                                                                             0 (81/4)                                                                            724 2480                                                                               3626                       164  L     .01      298    2.5   -5/8  -1/2 853 2793                                                                               4116                       165  L     .025     292    3.3   -3/4  -1/2 875 2819                                                                               4297                       166  L     .05      292    3.4   -1/4  -3/8 908 2855                                                                               4330                       167  M     .01      300    2.5   -1/4  0    841 2629                                                                               4016                       168  M     .025     300    2.7   -1/8  -1/4 879 2722                                                                               4125                       169  M     .05      296    3.2   -1/8  -1/8 875 2844                                                                               4403                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE IX                                     __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     170  NONE  0        326    1.9   0 (6) 0 (81/4)                                                                            622 2069                                                                               3541                       171  N     .01      323    2.0   0     -3/8 610 2010                                                                               3488                       172  N     .025     324    2.0   -3/8  -3/8 615 2072                                                                               3610                       173  N     .05      318    2.2   -1/2  -3/4 643 2163                                                                               3894                       174  N     .10      320    2.3   -3/4  -7/8 663 2241                                                                               3942                       175  O     .01      317    2.1   -1/8  -1/2 627 2226                                                                               3666                       176  O     .025     316    2.5   -1/2  -1/2 658 2255                                                                               3790                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE X                                      __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     177  NONE  0        307    2.1   0 (55/8)                                                                             0 (8)                                                                               --  2609                                                                               3752                       178  P     .035     300    2.8   +1/2  0    --  2699                                                                               3965                       179  P     .065     302    2.7   +1/2  +1/4 --  2731                                                                               3899                       180  Q     .035     309    2.7   +1/2  +1/4 --  2384                                                                               3552                       181  Q     .065     294    3.8   +1/4  0    --  2725                                                                               4187                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE XI                                     __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     182  NONE  0        312    1.8   0 (61/4)                                                                             0 (81/2)                                                                            602 --  3563                       183  P     .05      297    2.4   -1/8  -1/4 696 --  4404                       184  P     .025     302    2.3   -1/4  -5/8 707 --  4324                       185  P     .0375    297    2.6   -1/4  -3/8 713 --  4479                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE XII                                    __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     186  NONE  0        317    1.9   0 (6) 0 (77/8)                                                                            682 2363                                                                               3933                       187  Q     .025     310    2.5   -1/8  +1/8 710 2390                                                                               4163                       188  Q     .05      309    2.9   -1/4  +1/8 715 2428                                                                               4274                       189  Q     .075     308    3.3   0     -1/8 691 2432                                                                               4285                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE XIII                                   __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     190  NONE  0        307    2.1   0 (55/8)                                                                             0 (8)                                                                               --  2609                                                                               3752                       191  P     .035     300    2.8   +1/2  0    --  2699                                                                               3965                       192  P     .065     302    2.7   +1/2  +1/4 --  2731                                                                               3899                       193  Q     .035     309    2.7   +1/2  +1/4 --  2384                                                                               3552                       194  Q     .065     294    3.8   +1/4  0    --  2725                                                                               4187                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE XIV                                    __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     195  NONE  0        329    1.8   0 (45/8)                                                                             0 (61/4)                                                                            1121                                                                               3586                                                                               5265                       196  P     .025     315    2.5   +3/8  +1/8 1335                                                                               4044                                                                               5863                       197  Q     .025     317    2.7   +3/8  +1/8 1218                                                                               3909                                                                               5634                       198  R     .025     314    3.6   +3/8  +1/4 1290                                                                               3935                                                                               5769                       199  Q     .05      320    3.1   +1/8  0    1416                                                                               4073                                                                               5793                       200  R     .05      316    4.3   0     -1/8 1343                                                                               3813                                                                               5440                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE XV                                     __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     201  NONE  0        316    1.9   0 (61/8)                                                                             0 (83/8)                                                                            625 2088                                                                               3816                       202  S     .01      299    3.3   0     0    713 2313                                                                               4191                       203  S     .025     291    4.1   -1/4  -1/8 729 2310                                                                               4260                       204  S     .05      288    4.9   -1/8  +1/8 719 2335                                                                               4174                       205  T     .01      303    2.2   -1/8  -1/8 743 2416                                                                               4190                       206  T     .025     298    2.3   0     -1/8 744 2341                                                                               4260                       207  T     .05      299    2.6   -1/8  -1/4 744 2306                                                                               4223                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+ ) sign.                      

                                      TABLE XVI                                    __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     208  NONE  0        314    2.1   0 (53/4)                                                                             0 (73/4)                                                                            856 --  3693                       209  T     .01      308    2.4   0     -1/4 943 --  3819                       210  T     .025     312    2.3   0     -1/4 950 --  3869                       211  T     .05      312    2.3   +3/8  +1/4 968 --  3949                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

                                      TABLE XVII                                   __________________________________________________________________________                                      Rate of Hardening                                                              Relative to                                                                               Compressive Strength;                                  Water        Plain (None) Mix.sup.1                                                                    p.s.i.                                        Dose; percent by                                                                        lbs/cu.yd    Hours      (MPa)                              Mix No.                                                                             Additive                                                                             weight of cement                                                                        (kg/cu/mtr)                                                                           Air Vol. %                                                                           Initial Set                                                                          Final Set                                                                           1 day                                                                              7 day                                                                              28 days                    __________________________________________________________________________     212  NONE  0               1.8   0 (5) 0 (7)                                                                               1278                                                                               4023                                                                               5047                       213  U + TEA                                                                              .05 + .005      2.5   0     -1/4 1182                                                                               4083                                                                               5321                       214  U     .01             2.2   -1/8  -1/4 1327                                                                               4274                                                                               5190                       215  U     .025            2.2   -1/8  -1/8 1344                                                                               4422                                                                               5324                       216  U     .05             2.6   0     0    1282                                                                               4414                                                                               5264                       217  U     .10             3.0   -1/8  -1/4 1232                                                                               4526                                                                               5541                       __________________________________________________________________________      .sup.1 Acceleration of rate of hardening is indicated by a minus (-) sign      while retardation is indicated by a plus (+) sign.                       

It is within the scope of the invention to incorporate, in the cement mixes prepared as herein provided, other additives known in the art for the express purpose for which they are normally employed. Such other additives may, for example, be air-entraining agents, air-detraining agents, pozzolanic materials, fly ash coloring agents, water repellants, other strength enhancing admixtures and the like. The admixtures of the present invention may also be employed in conjunction with a combination of such cement additives to produce desired changes in the physical properties of the concrete being produced.

It is also within the scope of the invention to employ the admixture of the present invention together with known set retarders, such as lignosulfonates, sugars, glucosaccharides, and the like, or combinations thereof to obtain improvement in the compressive strength of the hardened mix, but less retarding effect than would result from such set retarders. The admixtures of the present invention can also be employed together with conventional set accelerators as mentioned above to achieve a desired combination of benefits.

While the invention has been described with reference to certain preferred embodiments thereof, those skilled in the art will appreciate that various changes and modifications and subsitutions can be made without departing from the spirit of the invention. It is intended, therefor, that the invention will be limited only by the scope of the claims which follow. 

What is claimed is:
 1. A hydraulic cement mix comprising a hydraulic cement, aggregate in an amount of up to 80 percent by weight based upon the total weight of said cement mix, sufficient water to effect hydraulic setting of the cement, and an additive selected from the group consisting of poly(hydroxyalkylated)polyamine, alkoxylated poly(hydroxyalkylated)polyamine hydroxyalkylated derivatives of the compounds hydrazine, 1,2-diaminopropane, and polyglycoldiamine, and mixtures thereof, said additive being present in an amount sufficient to increase the compressive strength of the hardened mix.
 2. A hydraulic cement mix in accordance with claim 1, wherein said hydraulic cement comprises portland cement.
 3. A hydraulic cement mix in accordance with claim 1, wherein said additive is present in an amount of up to 0.025% by weight based upon the weight of the cement.
 4. A hydraulic cement mix in accordance with claim 1, wherein said additive is present in an amount of between about 0.005% and about 0.25% by weight based upon the weight of the cement.
 5. A hydraulic cement mix in accordance with claim 1, wherein said additive is present in an amount of between about 0.02% and about 0.07% by weight based upon the weight of the cement.
 6. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises an 8:1 mole ratio of propyleneoxide to diethylenetriamine.
 7. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises di(hydroxyethyl)1,2-diaminopropane.
 8. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises tetra(hydroxyethyl)1,2-diaminopropane.
 9. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises di(hydroxyethyl)hydrazine.
 10. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises tetra(hydroxyethyl)hydrazine.
 11. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises a 5:1 mole ratio of ethylene oxide to ethylenediamine.
 12. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises a 6:1 mole ratio of ethylene oxide to ethylenediamine.
 13. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises an 8:1 mole ratio of ethylene oxide to ethylenediamine.
 14. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises ethoxylated polyglycoldiamine.
 15. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises Ethoxylated Amine HH, having a typical analysis of: ##STR6##
 16. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises the condensate of a 2:1 mole ratio of diethanolamine to formaldehyde.
 17. A hydraulic cement mix in accordance with claim 1, wherein said additive comprises penta(hydroxyethyl)diethylenetriamine.
 18. A hydraulic cement mix in accordance with claim 1, wherein the additive has the following formula:

    (R').sub.2 NCH.sub.2 CH.sub.2 N(R').sub.2

wherein R is (CH₂ CH₂ O)_(y) H, wherein y is selected from 0, 1 or 2, wherein no more than one-half (1/2) of the y's are equal to 0, and each R can be the same or different.
 19. A hydraulic cement mix in accordance with claim 18, wherein the additive is selected from the group consisting of an 8:1 mole ratio of propyleneoxide to diethylenetriamine; a 5:1 mole ratio of ethylene oxide to ethylenediamine; a 6:1 mole ratio of ethylene oxide to ethylenediamine; and a 8:1 mole ratio of ethylene oxide to ethylenediamine.
 20. A hydraulic cement mix in accordance with claim 1 wherein the additive has the general formula: ##STR7## wherein R" is selected from the group of (CH₂ CH₂ O)_(y) H and ##STR8## wherein X is a covalent bond or a divalent organic radical selected from the group of CH₂, CH₂ CH₂, ##STR9## and CH₂ CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ CH₂ ;wherein y and v are selected from the group of 0, 1 and 2; wherein w is selected from the group of 0 and 1; wherein v and w cannot both be 0; and wherein no more than one-half (1/2) of the R" groups are hydrogen.
 21. A hydraulic cement mix in accordance with claim 20, wherein the additive is selected from the group consisting of an 8:1 mole ratio of propyleneoxide to diethylenetriamine; di(hydroxy-ethyl)1,2-diaminopropane; tetra(hydroxyethyl)1,2-diaminopropane; di(hydroxyethyl)hydrazine; tetra(hydroxyethyl)hydrazine; a 5:1 mole ratio of ethylene oxide to ethylenediamine; a 6:1 mole ratio of ethylene oxide to ethylenediamine; an 8:1 mole ratio of ethylene oxide to ethylenediamine; ethoxylated polyglycoldiamine; ethoxylated amine; and the condensate of a 2:1 mole ratio of diethanolamine to formaldehyde.
 22. A hydraulic cement mix in accordance with claim 1, wherein said aggregate is present in an amount of from 20% to 80% by weight.
 23. A process for increasing the compressive strength of hardened hydraulic cement mixes which include hydraulic cement, aggregate in an amount of up to 80% by weight based upon the total weight of said cement mix, and sufficient water to effect hydraulic setting of the cement, comprising incorporating an additive of the general formula: ##STR10## wherein R" is selected from the group of (CH₂ CH₂ O)_(y) H and ##STR11## wherein X is a covalent bond or a divalent organic radical selected from the group of CH₂, CH₂ CH₂, ##STR12## and CH₂ CH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ OCH₂ CH₂ CH₂ ;wherein y and v are selected from the group of 0, 1 and 2; wherein w is selected from the group of 0 and 1; wherein v and w cannot both be 0; and wherein no more than one-half (1/2) of the R" groups are hydrogen.
 24. A process in accordance with claim 23, wherein said hydraulic cement comprises portland cement.
 25. A process in accordance with claim 23, wherein the said additive is present in an amount of up to 0.25% by weight based upon the weight of the cement.
 26. A process in accordance with claim 23, wherein the said additive is present in an amount of between about 0.01% and 0.5% by weight based upon the weight of the cement.
 27. A process in accordance with claim 23, wherein the said additive is present in an amount of between about 0.01% and 0.1% by weight based upon the weight of the cement.
 28. A process in accordance with claim 23, wherein said additive is present in an amount of between 0.02% and 0.07% by weight based upon the weight of the cement.
 29. A process in accordance with claim 23, wherein said additive comprises tetra(hydroxyethyl)ethylenediamine. 